Scouring agents with a bleaching and disinfecting action

ABSTRACT

SCOURING AGENTS HAVING A BLEACHING AND DISINFECTING ACTION COMPRISING A MAJOR AMOUNT OF WATER-INSOLUBLE SCOURING COMPONENTS AND A MINOR AMOUNT OF ESSENTIALLY WATER-SOLUBLE COMPONENTS INCLUDING A SOLID WATER-SOLUBLE PER-COMPOUND AND AN EFFECTIVE AMOUNT OF ACYLATED GLYCOLURIL ACTIVATORS HAVING THE FORMULA   1-R2,3-R4,4-R3,6-R1,2,5-DI(O=)OCTAHYDROIMIDAZO(4,5-D)   IMIDAZOLE   WHEREIN AT LEAST TWO OF R1, R2, R3 AND R4 ARE ACYLS OF ORGANIC CARBOXYLIC ACIDS HAVING FROM 2 TO 8 CARBON ATOMS AND THE REMINDER OF R1, R2, R3 AND R4 ARE MEMBERS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL HAVING FROM 1 TO 8 CARBON ATOMS, PHENYL, PHENYLALKYL HAVING FROM 7 TO 8 CARBON ATOMS, AND ACYLS OF ORGANIC CARBOXYLIC ACIDS HAVING FROM 2 TO 8 CARBON ATOMS.

United States Patent O 3,630,921 SCOURING AGENTS WITH A BLEACHING AND DISINFECTING ACTION Karlheinz Disch, Hilden, Rhineland, Dieter Kuhling, Monheim, Rhiueland, Peter Krings, Krefeld, and Horst Bellinger, Dusseldorf, Germany, assignors to Henkel & Cie GmbH, Dusseldorf-Holthansen, Germany No Drawing. Filed Dec. 27, 1968, Ser. No. 787,623 Claims priority, application Germany, Dec. 3, 1968, P 18 12 382.5 Int. Cl. Clld 7/54 US. Cl. 252-95 4 Claims ABSTRACT OF THE DISCLOSURE Scouriug agents having a bleaching and disinfecting action comprising a major amount of water-insoluble scouring components and a minor amount of essentially water-soluble components including a solid water-soluble per-compound and an effective amount of acylated glycoluril activators having the formula wherein at least two of R R R and R are acyls of organic carboxylic acids having from 2 to 8 carbon atoms and the remainder of R R R and R are members selected from the group consisting of hydrogen, alkyl having from 1 to 8 carbon atoms, phenyl, phenylalkyl having from 7 to 8 carbon atoms, and acyls of organic carboxylic acids having from 2 to 8 carbon atoms.

THE PRIOR ART Cleaning and scouring agents which contain an additive with both a bleaching and disinfecting action are known already. In particular, bleaching and disinfecting detergents and scouring agents with a content of active chlorineliberating compounds have been described. However, since such substances have the disadvantage of emitting an unpleasant and lasting chlorine odor it has already been suggested to replace the active chlorine-liberating compounds by an odor-free active oxygen-liberating compound. However, this substitution gives rise to the necessity of adding an activator for the liberating of the active oxygen from the corresponding compound, since mostly such cleaning and scouring agents are supposed to display their entire effectiveness at low temperatures. All storable per-compounds which come into consideration as bleaching and disinfectant additives do not liberate sufficient active oxygen at these low temperatures. Therefore, cleaning and scouring agents with a content of per-compounds and an activator for the per-compound have already become known.

In accordance with German Auslegeschrift 1,280,456 the addition of an inert carrier substance impregnated with solutions of metal ions, particularly Co, Mn Ni Cr, M Cu is recommended. The disadvantages of these activators is that on the one hand a sequestration agent is required simultaneously, in order to avoid undesired discolorations caused by the mentioned metal ions, and on the other hand those condensated phosphates normally employed in cleanser, owing to their satisfactory cleansing action, with the exception of hexametaphosphate, decrease the catalytic effectiveness of the activator.

3,630,921 Patented Dec. 28, 1971 OBJECTS OF THE INVENTION An object of the present invention is the obtention of scouring agents having a bleaching and disinfecting action comprising a major amount of water-insoluble scouring components and a minor amount of essentially watersoluble components including a solid water-soluble percompound and an eifective amount of acylated glycol compound and an effective amount of acylated glycoluril activators having the formula DESCRIPTION OF THE INVENTION The present invention provides scouring agents having a bleaching and disinfecting action comprising a major amount of water-insoluble scouring components and a minor amount of essentially water-soluble components including a solid water-soluble per-compound and an effective amount of acylated glycoluril activators having the formula wherein at least two of the residues R to R represent acyls of organic carboxylic acids having from 2 to 8 carbon atoms, while the other residues represent hydrogen atoms and/or alkyland/or aryl-residues with 1 to 8 carbon atoms and/or acyls of organic carboxylic acids having from 2 to 8 carbon atoms. The acyl residues in the molecule may be the same or different. Preferably, tetra-acylated glycolurils with the same acyl residues of organic carboxylic acids having from 2 to 4 carbon atoms,

preferably alkanoic acids having 2 to 4 carbon atoms, are used.

Preferred are acylated glycoluril activators having the formula R5 is 1i H g C:0

wherein at least two R R R and R are acyls of carboxylic acids selected from the group consisting of alkanoic acids having from 2 to 4 carbon atoms and benzoic acid and the remainder of R R R and R are members selected from the group consisting of hydrogen, alkyl having from 1 to 8 carbon atoms, phenyl,

phenyalkyl having from 7 to 8 carbon atoms, alkanoyl having from 2 to 4 carbon atoms, and benzoyl.

Suitable acyl residues of organic carboxylic acids havfrom 2 to 8 carbon atoms are, for example, alkanoyls, such as acetyl, propionyl, butyryl, etc.: haloalkanoyls, such as monochloroacetyl, dichloroacetyl. trichloroacetyl, etc.; benzoyl and toluyl which may be substituted with nitro groups or halogen atoms; methoxybenzoyls; and nitrilobenzoyls. Suitable alkyls having 1 to 8 carbon atoms are, for example, methyl, ethyl, etc.

Tetraacetyl-glycoluril and its preparation are known. It is obtained by acetylating glycoluril with acetic acid anhydride. The other acylated glycolurils can be prepared in a similar way by reacting glycoluril with acetic acid anhydride. The other acylated glycolurils can be prepared in a similar way by reacting glycoluril with carboxylic acid anhydrides, carboxylic acid chlorides or carboxylic acid esters. Apart from tetraacetyl-glycoluril, the activators employed in the washing agents of the present invention are new chemical components, and are the subject of copending commonly-assigned U.S. application No. 787,597 filed concurrently herewith and entitled Acylated Glycolurils as Activators for Per-Compounds.

Among the preferred acylated glycolurils can be mentioned the following: tetraacetyl-glycoluril, tetrapropionyI-glycoluril, tetrabutyryl glycoluril, 1.3 dimethyl- 4,6 diacetyl glycoluril, l methyl 3.4.6 triacetylglycoluril, diacetyl dipropionyl glycoluril. 1.3 dimethyl 4 acetyl 6 propionyl glycoluril. diacetyldibenzoyl-glycoluril. The alkyl and aryl substituted glycolurils may be produced by condensation of glyoxal with the alkyl or aryl substituted ureas. Any of the above acylated glycolurils may be substituted for the tetraacetyl-glycoluril and tetrapropionyl-glycoluril utilized in the examples with comparable activation of the active oxygen. taking into account the fact that a larger amount of a diacylated or triacylated glycoluril must be utilized in replacement of a tetraacylated glycoluril.

The quantitative ratio between the acylated glycoluril activator and the per-compound should be selected so that from 10 to 0.1 particularly from 4 to 0,2 N-acyl groups are available per molecule of organically or inorganically bound H Particularly advantageous is the usage of tetraacylated glycolurils.

The composition of the scouring agents of the invention preferably lie within the scope of the following general recipe.

60% to 95% preferably 80% to 90% by weight of water-insoluble scouring components, 40% to preterably 20% to by weight of an essentially watersoluble mixture consisting of:

5% to 100%, preferably 10% to 50% by weight of a combination of per-compound and activator of the above specified constitution, whereby the quantitative ratio between per-compound and activator lies within the above range,

0 to 95%, preferably 10% to 60% by weight of anionic,

nonionic and/or amphoteric surface active agents.

0 to 95%, preferably 10% to 50% by weight of alkaline reacting inorganic builders and organic complex formers.

0 to preferably 1% to 10% by weight of other common scouring agent components.

Useful as water-insoluble scouring components are mineral finely-ground materials such as quartz. feldspar, marble or fiuor-spar powder, kaolin and pumice stone. In place of mineral ground materials, finely-ground synthetic resin granulates or their mixtures with mineral scouring components may be used. Also mineral ground materials coated with a synthetic resin film may be used.

The per-compounds used in the scouring agents of the invention may be of an organic or inorganic nature. Suitable are. for instance, per-compounds such as urea and malamine perhydrate and in particular inorganic per salts Cal such as, for instance, alkali metal perborates, percarbonates, perpyrophosphates and persilicates. Among those preferably inorganic per salts to be used, sodium perborate tetrahydrate is of specific practical importance. Instead may as well be used partially or completely dehydrated perborates. that is dehydrated to the approximate composition: NaBO -H O Finally, borates NaBO -H O containing active oxygen, in which the proportions Na O:B O is less than 05:1 and is preferably in the range from 0.4 to 0.15:1, and in which the proportions il O zNa is in the range from 0.5 to 4:1 are also useful. These products are described in the German Pat. No. 901.287 and in the US. Pat, No. 2,491,789.

The perborates may be wholly or partly replaced by the above-identified inorganic per-compounds. These peroxyhydrates are preferably soluble in water and are ordinarily utilized in the form of their alkali metal salts, such as their sodium salts.

The anionic. amphoteric or non-ionic surface-active compounds contain in the molecule at least one hydrophobic residue containing 8 to 26, preferably 10 to 20 and in particular 12 to 18 carbon atoms and at least one anionic or non-ionic or amphoteric water-solubilizing group. The advantageously hydrophobic residue may be of aliphatic or alicyclic nature, and be combined with the water-solubilizing groups directly or through intermediate members. Suitable intermediate members are, for example, benzene rings, carboxylic acid ester or carbonamide groups ether or ester-like bound residues of polyvalent alcohols, such as ethylene glycol or propylene glycol, glycerine or corresponding polyether residues.

The hydrophobic residue is preferably an aliphatic hydrocarbon residue with 10 to 18 carbon atoms, but deviations from this preferred carbon range are possible depending on the nature of the surface-active compound in question.

Soaps are useful as anionic detergents which are derived from natural or synthetic fatty acids, and possibly also from resin or naphthenic acids, particularly, if these acids have iodine numbers of 30 at the most and preferably of less than 10.

Of the synthetic anionic surface-active compounds, the sulfonates and sulfates are of special practical importance.

The sulfonates include, for example, the alkylaryl sulfonates, especially the alkyl benzene sulfonates, which are obtained among others from preferably straight-chain aliphatic hydrocarbons with 9 to 15, preferably 10 to 14 carbon atoms by chlorination with alkylation of benzene or from corresponding olefins with terminal or non-terminal double bonds by alkylation of benzene and sulfonation of the alkylbenzenes obtained. Further, aliphatic sulfonates are of interest, such as, for example, are obtainable from preferably saturated hydrocarbons containing 8 to 18 and preferably 12 to 18 carbon atoms in the molecule by sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen and conversion of the products thereby obtained into the sulfonates. Furthermore, mixtures of alkenesulfonates, hydroxyalkenesulfonates and disulfonates, such as are obtained. for example from terminal or central C C and preferably C C olefins by sulfonation with sulfur trioxide and acid or alkaline hydrolysis of the sulfonate products, are utilizable as aliphatic sulfonates. In the aliphatic sulfonates so prepared, the sulfonate group is often found on a secondary carbon atom, but by reacting terminal olefins with bisulfite, sulfonates with terminal sultonate groups, may be prepared.

Salts, preferably dialkali salt of a-sulfo-fatty acids as well as salts of esters of these acids with alcohols containing l to 4 and preferably 1 or 2 carbon atoms also belong to the sulfonates to be used according to the inventiOn.

Further utilizable sulfonates are the fatty acid esters of hydroxyethanesulfonic acid and dihydroxypropanesulfonic acid, the salts of fatty alcohol esters of lower aliphatic or aromatic sulfo-monoand di-carboxylic acids containing 1 to 8 carbon atoms, the alkylglycerylethersulfonates, aswe ll as the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.

Suitable surface-active compounds of the sulfate type are fatty alcohol sulfates, especially those derived from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol. Useful sulfonation products of the sulfate type can also be prepared from C to C olefins with terminal or nonterminal double bonds. Furthermore, this group of surface-active compounds includes sulfated fatty acid alkylolamides, sulfated monoglycerides and sulfated products of ethoxylated and/or propoxylated fatty alcohols, alkylphenols with 8 to 15 carbon atoms in the alkyl residue, fatty acid amides, fatty acid alkylolamides and so on, where 0.5 to 20, preferably 1 to 8, and especially 2 to 4 mols of ethylene oxide and/or propylene oxide are added on to one mol of the said compounds to be ethoxylated and/or propoxylated.

Suitable as anionic surface-active agents of the carboxylate type are, for example, the fatty acid esters or fatty alcohol ethers of hydroxy carboxylic acids as well as the amide-like condensation products of fatty acids or sulfonic acid with amino carboxylic acids, for example, with glycocol, sarcosine or albumin hydrolysates.

The non-ionic surface-active agents useful in the scouring agents are the so-called Non-ionics which are products which owe their water solubility to the presence of polyether chains, amineoxide, sulfoxide or phosphineoxide groups, alkylolamide groupings as well as in general to a large number of hydroxyl groups.

Of special practical interest are products which are obtainable through the addition of ethyleneoxide and/or glycide to fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid or sulfonic acid amides. These Nonionics may contain from 2 to 100, preferably 6 to 40 and especially 8 to 20 ether radicals, and above all ethyleneglycolether radicals per molecule. Furthermore, these polyether radicals may contain central or terminal propyleneor butyleneglycolether radicals or polyether chains.

Watersoluble addition products of ethyleneoxide to water-insoluble propyleneglycols which are known commercially under the name of Pluronics, Tetronics or Ucon Fluid," as well as addition products of propyleneoxide to alkylenediamines or to lower aliphatic alcohols containing from 1 to 8 and preferably 3 to 6 carbon atoms are also classed as Non-ionics. These water-insoluble propyleneoxide derivatives represent the hydrophobic residue.

Other suitable Non-ionics are fatty acid or sulfonic acid alkylolamides which are derived, for instance, from monoor diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, e.g., the glycamines. They may be replaced by amides from higher primary or sec. alkylarnines and polyhydroxycarboxylic acids.

To the capillary active amineoxides belong, for instance, those products which are derived from higher tert. amines which possess a hydrophobic alkyl radical and two shorter alkyl and/ or alkylol radicals 'with up to 4 carbon atoms each.

Amphoteric surface-active agents contain both acid and basic hydrophile groups in the molecule. Among the acid groups are carboxylic acid groups, sulfonic acid groups, sulfuric acid half ester groups, phosphonic acid groups and phosphoric acid partial ester groups. Among the basic groups are primary, secondary, tertiary and quaternary ammonium groupings.

OWing to their good compatibility with other surfaceactive agents, carboxy, sulfate and sulfonate betaines are of special practical interest. Suitable sulfobetaines are obtained, for instance, through reaction of tert. amines, containing at least one hydrophobic alkyl radical, with sultones, for instance, propane or butane sultone. Corresponding carboxybetaines are obtained through reaction of the above-identified tert. amines with chloroacetic acid, its salts or with chloroacetic acid esters and cleavage of the ester bond.

The foaming properties of the surface-active agents may be increased or decreased by means of combination of suitable surface-active agent types as well as being modified by addition of non-surface-active organic substances. Particularly well suited as foam stabilizers for surface-active agents of the sulfonate or sulfate type are capillary active carboxy or sulfobetaines as well as the above-identified non-ionics of the alkylolamide type. Equally well suited for this purpose are fatty alcohols or higher terminal alkanediols.

Suitable alkaline-reacting builders are, for instance, the bicarbonates, carbonates, borates or silicates of the alkali metals, mono-, dior trialkali orthophosphates dior tetra alkali pyrophosphates, alkali metal tripolyphosphates as well as the alkali metal metaphosphates known as complex-forming compounds. Usable organic complexforming compounds, are, for example, the alkali metal salts of hydroxy'car'boxylic acids such as the salts of lactic acid, citric acid and tartaric acid. Other usable organic complex-forming compounds are the alkali metal salts of nitr-ilotriacetic acid, ethylenediaminetetraacetic acid, N- hydroxyethylethylenediaminetriacetic acid, polyalkylenepolyamine-N-polycanboxylic acids as well as other known organic complex-forming compounds. Combinations of several complex-forming compounds may be employed as well. Diand poly-phosphonic acids of the following constitutions also belong to the other known complex-forming compounds:

in which R represents alkyl and R represents alkylene residues with l to 8, preferably 1 to 4, carbon atoms, and X and Y represent hydrogen atoms or alkyl with 1 to 4 carbon atoms. Carboxy-methylenephosphonic acid is also useful as a complex-forming compound according to the invention. All these complex-forming compounds may be present as free acids, but it is preferred to use them as their alkali metal salts.

The above alkaline-reacting inorganic builders and organic complex-forming compounds may partly be replaced by neutrally-reacting diluents, for example, sodium sulfate or sodium chloride.

Among the other commonly known scouring agent components are dirt-dispersing colloids such as watersoluble cellulose derivatives or water soluble salts of higher molecular weight polycarboxylic acids, particularly polymerizates of maleic acid, acrylic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Usable as dirt-dispersing colloids as well are mixed polymerizates of these latter acids among themselves or with other polymerizable substances such as, for instance. with ethylene. propylene, acrylic acid, methacrylic acid. crotonic acid. 3-butenecarboxylic acid. 3 methyl-3-butenecarboxylic acid as well as vinylmethylether, vinyl acetate. isobutylene. acrylamide and styrene. Other scouring agent components comprise antimicrobial substances. skin-protective substances or super-fatting agents, corrosion inhibitors. enzymes possibly coated or stabilized as well as dyestuffs and perfumes.

The compositions of some of the prepa ations of the present invention will be further described by way of reference to the following examples. These are. however, not to be deemed limitative in any respect.

EXAMPLES The salt components. salt of surface-active agents. other organic salts as well as inorganic salts which are contained therein, are sodium salts. The terms used in the examples are as follows:

Alkylbenzenesulfonate" represents the sodium salt of an alkylbenzenesulfonic acid with from to 15. preferably ll to 13 carbon atoms in the alkyl chain which is obtained by condensation of straight-chain olefins with benzene and sulfonation of the thus obtained alkylbenzene.

Fatty alcohol-t-EO" represents the addition products of ethylene oxide (E0) to technical oleyl alcohol. The

number indicates the molar amount of ethylene oxide added per 1 mol of alcohol.

Olefinsulfonate" represents a sulfonate obtained from olefin mixtures with from 12 to 18 carbon atoms through sulfonation with 50;; and hydrolyzation of the sulfonation product with sodium hydroxide solution. This sulfonate mainly consists of alkenesulfonates and hydroxyalkanesulfonates as well as small amounts of disulfonates. Each of the olefinsulfonate containing preparations was prepared from two different olefinsulfonate types: one of these had been prepared from a mixture of straight-chain terminal olefins, the other from a mixture of non-terminal olefins.

Fatty alcohol-ZEO-sulfate" represents a sulfated addition product of 2 mols of ethyleneoxide to 1 mol of coconut fatty alcohol.

Fatty alcohol sulfate" represents a sulfated coconut fatty alcohol. Fatty acid diethanol amide" represents the amide from coconut fatty acid and diethanolamine.

Alkanesulfonate represents a sulfonate obtained from parafiins with from 12 to 16 carbon atoms by means of sulfoxidation.

Soap represents the sodium salts of a fatty acid mixture of the following composition:

20% C fatty acids 12% C -fatty acids C fatty acids and 43% C fatty acids Perborate" represents an approximate oxygen containing product of the approximate NaBoz H202 active The explanations for the remaining terms can be taken from the above context whereby the expression fatty acid is always to be interpreted as coconut fatty acid mixture.

Example 1 Percent by wt. Alkylbenzenesulfonate Fatty alcohol-H0 EO Pyrophosphate 1 Sodium carbonate Perborate Tetraacetyl-glycoluril Quartz powder 88.

Example 2 Percent by wt. Olefinsulfonate 4 \onylphenol ltl EO 0.5 Tripolyphosphate 2 Perborate 2 l .3-dimethyl-4.6-diacetyl-glycoluril 2 Quartz powder 89.5

Example 3 Percent by wt. 1-\lltylbenzencsulfonate 2.5 Fatty alcohol sulfate 2 Borax 2 Perborate 2.5

TetrztpropzonyLglycoluril 2 \larble powder 89 Example 4 Percent by wt. Alkylbenzenesulfonate 3 Fatty alcohol-2 EO-sulfate 1 Fatty acid diethanolamide 0.5 Nitrilotriacetate 0.5

Perborate 3 l-methyl-3.4.6-triacetyl glycoluril 2 Quartz powder 40 Marble powder 50 Example 5 Percent by wt. Soap -a 4.5 Orthophosphate 3 Perborate 4 l.4-dimethyl-3.6-diacetyl-glycoluril 2 Quartz powder 86.5

Example 6 Percent by wt. Alltanesulfonate 3 Fatty alcoholl0 EO-sulfate l Bicarbonate 3.5

Perborate 4 Tetraacetyl-glycoluril 4 Quartz powder 84.5

Example 7 Percent by wt. Alkylbenzenesulfonate 2 Fatty alcohol sulfate 1 Sodium carbonate 3 Orthophosphate 2 Tripolyphosphate 2 Perborate 3 Diacetybdipropionyl'glycoluril 2 Quartz powder Example 8 Percent by wt.

Fatty alcohol sulfate 4 Nonylphenol- -3 EO-sulfate l Pyrophosphate 2.5 Sodium carbonate 1.5

Perborate 3.5

l .3-dimethyl-4acetyl-6propionylglycoluril 2 Marble powder 5O Pumice powder 35.5

Example 9 Percent by wt. Alkylbenzenesulfonate 3 Fatty acid monoethanolamide+8 EO 1 Ethylenediaminetetraacetate 0.5 Sodium carbonate 2 lerborate 2 Tetraacetyl-glycoluril 2 Quartz powder 89.5

10 Example 1 Example 13 Percent by wt. ()l fin lfonate 3 Scouring agents were prepared which in addition to 4% Fatty 1-4 Bo lfat 15 by weight of alkylbenzenesulfonate; 1% by weight of T ipolyphosphate 2 fatty alcohol-2 EO-sulfate; 2% by welght of tripolyphos- Perborate 2, 5 phate; 85% by weight of quartz powder contained i 2 gh f i gm f fifi ffiI 89 (a) 4% by weight of perborate; 4% by weight of tetraacetyl-glycoluril Example 11 (b) 2% by weight of perborate; 2% by weight of tetra- Percent by acetyl-glycoluril; 4% by weight of sodium sulfate Alkylbenzenesulfonate 5 (c) 1% by weight of perborate; 1% by weight of tetra- TrlRolyphosphate 2 acetyl-glycoluril; 6% by weight of sodium sulfate. Sodium sulfate 3 Pefbofate 2 With these scouring agents, other dispersions were pre- Tetraacetyl-glycoluril 2 pared which consisted of 3 parts of scouring agent and 2 Quartz Powder 86 parts of water, with which the bleaching test according to Example 12 Example 12 was carried out. Again comparison tests with analogously composed scouring agents were carried out. A preparation of a dispersion of the scouring agent ac- However, the activator was replaced respectively by a cording to Example 11 was made. This dispersion concorresponding amount of sodium sulfate. The following sisted of two parts water and 3 parts scouring agent. 3 Table II lists the results.

TABLE II Bleaching 1% perborate 2% perborate 4% perborate With With With ime acti- Without acti- Without acti- Without Stain in min. vator activator vator activator vator activator Coffee 0.5 a 4.5 3 4 2 4 1 3.5 4 2.5 4 2 3.5 2 2.5 3 1.5 3 1 3 Tea 0.5 2.5 3 2.5 3 2 3 1 2 3 2 2.5 1 5 3 2 1.5 2 1.5 2 1 2 Carrot juice 2 4. 5 6 4 6 3. 5 6 5 4 5 4 6 a 6 100 4 6 3.5 6 3 6 gm. each of this dispersion were applied on clay plates Example 14 which had been stained purposely with coffee or tea or carrot juice. The bleaching treatment was carried out at ring agents with differing contents of perborate and 20 C. After various durations of action, the scouring activator were tested in comparison to corresponding mixagent was rinsed off and the bleaching effect was recorded. tufes ith ut a tivator, as to the antimicrobial action in Complete bleaching effect was expressed by 1 and an una suspension test. The test germs were Escherichia coli and recognizable bleaching effect was expressed by 6. The Pseudomvnas aerllginvm- The following scouring agent values listed in the following table represent average Samples were tested: values and are calculated on the basis of three individual A scouring agent according to Example 1 determinations. A comparison test was carried out with a (b) A scouring agent with 1% by weight of Perborate, scouring agent of s1m1lar compos1t1on. However, the ac- 1% by weight of tetraacetyl glycoluril, 5% by Weight of tlvator'to be employed was replaced by equal amount sodium sulfate; other than that, the same composition as of sodium sulfate. The following table lists the results. thescouringagentofExample11.

BLE I (c) A scouring agent with 0.5% by weight of per- Bleachin borate, 0.5% by weight of tetraacetylglycoluril, 6% by welght of sodlum sulfate; otherwise the composition of Stain g fi f jglg the scouring agent of Example 11.

These scouring agent samples were diluted with water Coflee .2 i in a ratio of 1:1 and 10 gm. each of this dispersion were Tea g used in the suspension test. As comparative substances,

'1 '2 2, 5 scouring agents of similar composition, but where the acticmotjuice g '2 '2 vator had been replaced by equal amounts of sodium sul- 5 4 6 fate, were utilized. The following Table III lists the killing 5 6 times for the test germs used in minutes.

TABLE III Killing time in minutes 0.5% perborate 1% perborate 2% perborate With Without With Without With Without actiactiaetiactiactiacti- Test germs vator vator vator vator vator vator s 1 30 0.5 30 iitfi'fltfifi ttiiott;ifi fit'gaa iariij; 3.? 0.5 530 0.5 530 1 1 The preceding specific embodiments are illustrative of the practice of the invention. It is obvious, however, that other expedients known to those skilled in the art may be employed without departing from the spirit of the invention.

We claim: 1. Scouring agents having a bleaching and disinfecting action consisting essentially of:

(a) from 80% to 90% by weight of Water-insoluble finely ground mineral scouring components, (b) from 10% to 20% by weight of an essentially water-soluble mixture consisting of:

(1) from 10% to 50% by weight of a combination of solid Water-soluble alkali metal salts of inorganic per-compounds containing inorganic-bound H and an acylated glycoluril activator having the formula:

R it

R Ra

wherein at least two of R R R and R are acyls of carboxylic acids selected from the group consisting of alkanoic acids having from 2 to 4 carbon atoms and benzoic acid, and the remainder of R R R and R are members selected from the group consisting of alkyl having from 1 to 8 carbon atoms, alkanoyl having from 2 to 4 carbon atoms and benzoyl, said acylated glycoluril activators being present in said combination in an amount sufiicient to supply from 4 to 0.2 N-acyl groups per molecule of said bound H 0 (2) from 10% to 60% by weight of surface-active agents selected from the group consisting of anionic surface-active agents, non-ionic surfaceactive agents and amphoteric surface-active agents,

(3) from 10% to 50% by weight of alkaline-reacting inorganic builders selected from the group consisting of alkali metal bicarbonates, carbonates, borates, silicates, orthophosphates, pyrophosphates and metaphosphates and organic complex-forming compounds selected from the group consisting of alkali metal salts of hydroxycarboxylic acids, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N hydroxyethyethylenediaminetriacetic acid, polyalkylene-polyamine N polycarboxylic acids, diphosphonic acids, polyphosphonic acids and carboxy-methylenephosphonic acid, and

(4) from 1% to 10% by weight of other known common scouring agent components selected from the grou consisting of neutral inorganic salts and dirt-dispersing colloids selected from the group consisting of Water-soluble cellulose derivatives and Water-soluble salts of higher molecular weight polycarboxylic acids.

2. Scouring agents having a bleaching and disinfecting action consisting essentially of:

(a) from 60% to 95% by weight of water-insoluble,

finely ground mineral scouring components, (b) from 5% to 40% by weight of an essentially water-soluble mixture consisting essentially of:

(1) from 5% to 100% by weight of a combination of solid water-soluble alkali metal salts of inorganic per-compounds containing inorganic-bound 12 H 0 and an acylated glycoluril activator having the formula:

wherein at least two of R R R and R are acyls of organic carboxylic acids having from 2 to 8 carbon atoms, selected from the group consisting of alkanoic acids, haloalkanoic acids, benzoic acid, nitrobenzoic acid, toluic acid, nitrotoluic acid, methoxybenzoic and nitrilobenzoic acid, and the remainder of R R R and R are members selected from the group consisting of alkyl having from 1 to 8 carbon atoms and acyls of organic carboxylic acids having from 2 to 8 carbon atoms, selected from the group consisting of alkanoic acids, halo-alkanoic acids, benzoic acid, nitrobenzoic acid, toluic acid, nitrotoluic acid, methoxybenzoic acid and nitrilobenzoic acid, said acylated glycoluril activators being present in said combination in an amount sufiicient to supply from 10 to 0.1 N-acyl groups per molecule of said inorganic-bound H 0 2) from O to by weight of surface-active agents selected from the group consisting of anionic surface-active agents, non-ionic surfaceactive agents and amphoteric surface-active agents,

(3) from 0 to 95% by weight of alkaline-reacting inorganic builders selected from the group consisting of alkali metal bicarbonates, carbonates, borates, silicates, orthophosphates, pyrophosphates and metaphosphates and organic complex-forming compounds selected from the group consisting of alkali metal salts of hydroxycarboxylic acids, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, polyalkylene-polyamine-N- polycarboxylic acids, diphosphonic acids, polyphosphonic acids and carboxy-methylenephosphonic acid, and

(4) from 0 to 20% by weight of other common scouring agent components selected from the group consisting of neutral inorganic salts and dirt-dispersing colloids selected from the group consisting of water-soluble cellulose derivatives and water-soluble salts of higher molecular weight polycarboxylic acids.

3. The scouring agents as defined in claim 2 wherein R R R and R are acyls of alkanoic acids having from 2 to 4 carbon atoms.

4. The scouring agents as defined in claim 2 activators are selected from the group consisting of tetraacetylglycoluril and tetrapropionyl-glycoluril.

References Cited UNITED STATES PATENTS 3,187,004 6/1965 Slezak et al. 260-3097 3,203,960 8/1965 Gandon et al 260309.7 3,459,669 8/1969 Das et al. 20299 MAYER WEINBLATT, Primary Examiner US. Cl. X.R. 

